Organosilicon compounds containing phosphorus and nitrogen



United States Patent 3,202,633 ORGANOSHJCON COMPOUNDS CONTAINHIG PHQSPHURUS AND NITRGGEN Frank Felrete, Monroeville, Pa., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed July 25, 1960, Ser. No. 44,834 25 Qlairns. (Cl. 260-465) This invention relates to novel organosilicon compounds which contain phosphorus and nitrogen.

The compounds of this invention include hydrocarbonoxysilanes and siloxanes containing from one to three phosphinylidyne groups [i.e. groups having the formulaEP(O)] each of which is bonded to (1) one or two monovalent hydrocarbon groups or halogen-substituted monovalent hydrocarbon groups, (2) zero or one hydrocarbonoxy groups and (3) a nitrogen atom that is also bonded to a hydrocarbonoxysilyl or siloxysilyl group thru at least three carbon atoms of a divalent hydrocarbon group. Also included among the compounds of this invention are polymers produced by hydrolyzing and condensing those hydrocarbonoxysilaues and siloxanes of this invention wherein each phosphorus atom is bonded to a hydrocarbonoxy group.

The hydrocarbonoxysilanes of this invention are represented by the formula:

wherein Y is a monovalent hydrocarbon group or a halogen-substituted monovalent hydrocarbon group, R is a monovalent hydrocarbon group, R is a hydrogen atom or a monovalent hydrocarbon group, R" is a divalent hydrocarbon group, 111 has a value from 1 to 3 inclusive and is preferably one, 11 has a value from O to 2 inclusive, (m-|-n) has a value from 1 to 3 inclusive, p is 1 or 2, and each nitrogen atom is interconnected to the silicon atom through at least three carbon atoms.

, Illustrative of the monovalent hydrocarbon groups represented by Y, R and R in Formula 1 are the linear alkyl groups (for example the methyl, ethyl, propyl, butyl and stearyl groups), the cyclic alkyl groups (for example the cyclohexyl and cyclopentyl groups, the linear alkenyl groups (for example the vinyl and the allyl groups), the cyclic alkenyl groups (for example the cyclopentenyl and the cyclohexenyl groups), the aryl groups (for example the phenyl and naphthyl groups), the alkaryl groups (for example the tolyl group) and the aralkyl groups (for example the benzyl and beta-phenylethyl groups).

Illustrative of the divalent hydrocarbon groups represented by R" in Formula 1 are the linear alkylene groups (for example the trimethylene, --(CI-I and the octadecamethylene, (CI-l groups), the arylene groups (for example the naphthylene, C H and para-phenylene, C H groups); the cyclic alkylene groups (for example the cyclohexylene C I-I group); the alkarylene groups (for example the tolylene, CH C H group) and the aralkylene group (for example the CH (C H )CHCH CH group).

Illustrative of the halogen-substituted monovalent hydrocarbon groups represented by Y in Formula 1 are the linear haloalkyl groups (for example the chloromethyl, gamma-chloropropyl, delta-bromobutyl, omega-bromostearyl and the like), the cyclic haloalkyl groups (for example the chlorocyclohexyl and chlorocyclopentyl groups), the linear haloalkenyl groups (for example the chlorovinyl and the bromoallyl groups), the cyclic alkenyl groups (for example the bromocyclopentenyl and the bromocyclohexenyl groups), the haloaryl groups (for example the chlorophenyl and bromonaphthyl wherein'R is hydrogen and wherein R" contains at least 3 carbon atoms (and most preferably from 3 to 5 carbon atoms) interconnecting silicon and nitrogen but contains not more than 18 carbon atoms.

Illustrative of the hydrocarbonoxysilanes of this invention are:

The siloxanes of this invention contain a group represented by the formula:

d t P-N-R" SiO hr-v m 2 wherein Y, R, R, R", p, m, n, (m+n), and p have the above-defined meanings and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

Illustrative of the groups represented by Formula 2 are the groups having the formula:

ing a group representing the Formula 2 wherein R and Y each contain from 1 to 18 carbon atoms, R is hydrogen, R contains from 3 to 18, or more preferably from 3 to 5, carbon atoms and m is one.

The siloxanes of this invention include those siloxanes that are composed solely ofgroups represented by Formula 2 and also include those siloxanes that contain one or more groups represented by Formula 2 together with one or more groups represented by the formula:

wherein R has the above-defined meanings and x has a value from to 3 inclusive.

Illustrative of the groups represented by Formula 3 are: the SiO phenylsiloxy, methylsiloxy, dimethylsiloxy, methylethylsiloxy, trimethylsiloxy, diphenylsiloxy, vinyl- (methyl)siloxy, divinylsiloxy, methyldiphenylsiloxy, and dicyclohexylsiloxy groups and the like.

The hydrocarbonoxy silanes and siloxanes of this invention are advantageously prepared by reacting a silicon compound (i.e. a hydrocarbonoxysilane or a siloxane) having an amino group interconnected to silicon through a divalent hydrocarbon group with a phosphorus compound composed of a phosphinylidyne group which is bonded to (1) one or two monovalenthydrocarbon groups or halogen-substituted monovalent hydrocarbon groups, (2) zero or one hydrocarbonoxy groups and (3) a halogen atom. The reaction is represented by the skeletal equation:

wherein Y, R, R, R", p and m have the above-defined meanings, X is a halogen atom (preferably chlorine or bromine) and the free valences of the silicon atom bond the silicon atom (in the case of silanes) to at least one hydrocarbonoxy group or (in the case of siloxanes) to at least one siloxy group and any remaining free valences of the silicon atom bond the silicon atom to a monovalent hydrocarbon group.

The process is best carried out by forming reaction mixture of the silicon compound used as a starting material and the phosphorus compound used as a starting material and maintaining the reaction mixture at a temperature at which the desired reaction occurs, while continuously removing from the reaction zone the hydrogen halide [HX in Equation 4] as it is formed in the reaction.

The mole ratio of the phosphorus compound and the silicon compound employed in the reaction represented by the Equation 4 is not narrowly critical. Stoichiometric amounts, i.e., the relative molar amounts indicated by Equation 4 are preferred for efficient reaction and ease of product recovery. For example, one gram atom of the nitrogen-bonded hydrogen of the silicon compound desired to be displaced is preferred for each gram atom of phosphorus compound. The use of no more than the stoichiometric amount of the starting phosphorus compound is especially desirable where R in Equation 4 is a hydrogen atom in order to minimize the production of products having two phosphorus atoms bonded to each nitrogen atom.

The temperature at which the reaction represented by Equation 4 is conducted is not narrowly critical and can be varied in accordance with the speed of reaction desired. Temperatures of 20 C. to 300 C. are advantageous in providing a smooth reaction and high yields of products.

Temperatures below 20 C. can be employed if desired but the reaction rate is slowed. Temperatures above 300 C. can also be employed but the likelihood of reduced yields is greater and the expense of operating at such high temperatures is undesirable. The process is advantageously carried out at atmospheric pressure or at whatever pressures exist in the particular reaction vessel employed without purposely applying increased or reduced pressures (i.e. autogenous pressure). Sub-atmospheric or super-atmospheric pressures can be employed, however, if desired.

No catalysts are required to effect the reaction represented by Equation 4 although suitable catalysts such as tetramethyl ammonium chloride, trimethyl benzyl ammonium chloride and the like can be employed for whatever advantage they may provide. Solvents also are not required but under certain conditions are useful in simplifying the handling of the reaction mixture or reducing the reaction time by providing a homogeneous reaction mixture if such is not otherwise obtainable. If a solvent is employed xylene, toluene, benzene, methylethyl ketone, dimethyl formamide, and the like can be used. A solvent which dissolves the starting materials and the products but does not dissolve hydrogen halides is particularly useful in removing the hydrogen halides from the reaction zone. Such solvents include toluene, benzene, xylene, dimethyl formamide, and the like.

The hydrogen halide (HX) formed in the reaction represented by Equation 4 is preferably continuously removed from the reaction zone by any suitable method of which many are known. A particularly suitable method is to add to the reaction mixture a hydrogen halide acceptor in the approximate stoichiometric amounts based on the amount of hydrogen halide expected to be formed in the reaction. Tertiary amines (e.g., triethyl amine, pyridine, tributyl amine, and the like) are some of the excellent hydrogen halide acceptors. Such tertiary amines form salts with the hydrogen halide which salts are insoluble in the reaction mixture. Excess amounts of the acceptors over and above the stoichiometric amount is preferably employed to ensure the substantially complete removal of the hydrogen halide. Alternately, the hydrogen halide can be continuously removed by heating the reaction mixture to cause the hydrogen halide to be evolved from the reaction mixture. Although it is not necessary in order to obtain a product, it is preferable, no matter what particular technique is employed in removing hydrogen halide, to maintain the pH of the system above a pH of about 6 and below a pH of about 8. It is preferable to maintain the pH above about 6 to prevent decreased yields due to possible side reactions involving the hydrogen halide formed in the process. It is preferable to maintain the pH below about 8 to prevent possible side reactions involving the silicon compound (e.g. reactions between the silicon compound and strongly basic hydrogen halide acceptors in the event moisture is also present).

The compounds of this invention can be isolated at the completion of the reaction represented by Equation 4 by any suitable conventional means. Thus the relatively low boiling compounds of this invention (i.e., in general, the hydrocarbonoxysilanes) can be isolated by filtration to remove insoluble salts and fractional distillation of the filtrate. The relatively high boiling compounds of this invention (i.e., in general, the siloxanes) can be isolated by stripping foreign material, extraction, filtering and/or recrystallization. One or more of the various conventional means can be employed to isolate the compounds wherein Y, R, X and p have the above-defined meanings. The preferred starting phosphorus compounds are those wherein Y and R each contain from 1 to 18 carbon atoms and X is chlorine or bromine.

Illustrations of the phosphorus compound represented to silicon through at least three carbon atoms.

' carbonoxysilanes and siloxanes of this invention include both hydrocarbonoxysilanes and siloxanes that contain an amino group interconnected to silicon through a divalent-hydrocarbon group. The hydrocarbonoxysilanes used as starting materials in producing the hydrocarbonoxysilanes of this invention are represented by the formula:

nNn"]msi(R)3- m+n wherein R, R, R m, n and (m-i-n) have the abovedefined meanings and the nitrogen atom is interconnected Illustrative of these silanes are gamma aminopropyltriethoxysilane, para-aminophenyltrimethoxysilane, delta-aminobutyl(methyl) diethoxysilane, bis(N-ethyl-para-aminophenyl)diethoxysilane, N phenyl aminophenylethyldimethyl phenoxysilane (i.e.,

HN (G l-I C H CH CH Si (CH 00 1-1 tris (gamma-amino-isobutyl) ethoxysilane (i.e.,

(H NCH CH(CH CH SiOC H The siloxanes that are used as starting materials in producing the siloxanes of this invention contain a group that is represented by the formula:

wherein R, R, R", m, n and (m+n) have the abovedefined meanings and the nitrogen atom is interconnected to silicon through at least three carbon atoms. Illustrative of the groups represented by Formula 7 are the gamma aminopropylsiloxy, para aminophenylsiloxy, delta-aminobutyl(methyl)siloxy, bis(N-ethyl-para-aminophenyl)siloxy, N-phenyl-aminophenylethyldimethylsiloxy H (i.e. C H51 ICaH CH CH SKCHahO) tris (gamma-aminoisobutyl) siloxy (i.e.

(H NCH CH(CH CH SiO) groups and N-ethyl-gamma-aminopropylsiloxy groups and the like.

Suitable starting siloxanes include both those siloxanes that are composed solely of groups represented by Formula 7 and those siloxanes that contain one or more groups represented by Formula 7 together with one or more groups represented by Formula 3.

The polymers of this invention that are produced by hydrolyzing and condensing those hydrocarbonoxysilanes and siloxanes of this invention wherein each phosphorus atom is bonded to a hydrocarbonoxy group (i.e. those silanes and siloxanes of this invention wherein p in the Formula 1 or 2 is one) contain a group that is represented by the formula:

Y o R an any] i.

0.5 111 wherein Y, R, R, R m, n and (m+n) have the abovedefined meanings. In such groups each phosphorus atom provides a link in the polymeric chain.

The silicon atom in the group represented by the Formula 8 can be linked through oxygen only to silicon or phosphorus or can be linked through oxygen to both silicon and phosphorus of another group or groups represented by Formula 8 to provide links in the polymeric chain. Each phosphorus atom in Formula 8 can be linked through oxygen atom to either silicon or phospohrus of another group represented by Formula 8 to provide a link in the polymeric chain. Such polymeric chains can be cyclic or can be terminated by hydroxyl or hydrocarbonoxy groups linked to a silicon atom or to the phosphorus atom. Such polymeric chains can also be terminated by an R SiO group linked to a silicon atom in the group represented by Formula 8.

When the phosphorus atom in the group represented by Formula 8 is linked through oxygen to a silicon atom of another group represented by Formula 8, the groups so linked can be depicted (in the case where m is one and n V 0.5 O R: (8!!) Where Y, R, R and R" have the above-defined meanings.

Illustrative of the polymers of this invention that contain a group represented by Formula 8 are the polymers which can be produced by the hydrolysis and condensation of the silane.

CH3 0 CH3 H3 PNCHgCHg-CHg-S iO 02115 C2H5O CH:

Such polymers are composed of the groups silane or siloxane of this invention that contain a POR group with water to hydrolyze the POR and, if any, SiOR groups in the former compounds to form POH groups and SiOH groups which condense to form the polymer. The amount of Water employed in the hydrolysis and condensation is at least one mole for each mole. of Si-OSi, SiO-P and POP linkages desired to be produced (i.e., one mole of water for each two moles of silicon-bonded and/or phosphorus-bonded hydrocarbonoxy group desired to be hydrolyzed to form siliconbonded hydroxyl groups which condense with each other to form the SiO-Si, SiOP or POP linkages). A small excess of water over and above this amount is preferred for speed and ease of reaction. Of course, silicon-bonded and phosphorus-bonded hydrocarbonoxy groups can be present in the polymer, if desired, by insation is effected by using a large excess of water and short reaction times in the hydrolysis and condensation. The hydrolysis and condensation reactions whereby are produced polymers containing groups represented by Formula 8 can be conducted at temperatures from C. to 250 C. Temperatures in the range of about 50 C. to 150 C. are preferred in order to hasten the hydrolysis and condensation without thermal decomposition. A solvent is preferably employed to provide ease of handling the reaction mixture. Suitable solvents are the liquid hydrocarbons, (e.g., toluene, benzene, xylene and the like), alcohols (e.g., ethanol, iso-propanol and the like) and ethers (e.g., diisopropyl ether, diethyl ether and the like.

In producing polymers containing groups represented by Formula 8, it is desirable, particularly where the hydrocarbonoxy group represented by OR is of relatively high molecular weight, to accelerate the rate of the hydrolysis and condensation reaction by employing a catalyst. By way of illustration, from about 0.5 to 3 percent by weight (based on the water reacted) of an inorganic acid (such as hydrochloric acid or sulfuric acid) can be used as a catalyst.

The polymers of this invention that contain groups that are represented of Formula 8 can be isolated by conventional means. Thus, after completion of the hydrolysis and condensation, low boiling materials such as wa ter, alkanol by-products, solvents and the like can be removed from the reaction mixture by conventional means (e.g. distillation at reduced pressure).

It should be understood that polymers containing groups represented by Formula 8 are mixtures of compounds and from which can be separated (e.g., by extraction or fractional crystallization) compounds containing only a particular type grouping (e.g. phosphorus combined only in POP or only in PO Si linkages).

The polymers of this invention that contain groups represented by Formula 8 can also contain one or more groups represented by Formula 3. The latter groups are present in these polymers when silanes having the formula R Si(OR) where R and x have above-defined meanings are cohydrolyzed and cocondensed along with a suitable (i.e. P-OR containing) silanes or siloxanes of this invention in the production of the polymers. Alternately a group or groups represented by Formula 3 are present in the polymer if suitable starting siloxanes of this invention are employed that contain a group or groups represented by Formula 3.

When suitable starting siloxanes of this invention are employed in producing polymers containing groups represented by Formula 8, (i.e., those containing P-OR groups), little or no Si-OR or SiOH groups may be initially present to react to form ESi0P linkages. However, ESi-OSlE linkages in the siloxane can react with the water and alcohol (i.e. the alcohol formed by the hydrolysis of POR) to produce SiOR and/or Si-OH. The presence of POH groups catalyzes such reactions of the normally stable SiOSi linkage.

Phosphorus-bonded monovalent hydrocarbon and halogen-substituted monovalent hydrocarbon groups have greater hydrolytic stability than phosphorus-bonded hydrocarbonoxy groups. Consequently, when a silane of this invention represented by Formula 1 wherein p is two is hydrolyzed and condensed according to the abovedescribed procedure, the product is the corresponding siloxane of this invention containing two phosphorusbonded monovalent hydrocarbon groups or halogensubstituted monovalent hydrocarbon groups.

The compounds of this invention are useful as lubri cants and as additives to lubricants for improving the lubricity thereof. In particular they can be added to organopolysiloxane lubricating fluids for imparting improved lubricity thereto. The siloxanes containing groups represented by Formula 2 and the polymers containing groups represented by Formula 8 are also useful as flame and solvent resistant protective coatings, particularly on metals such as steel, copper and aluminum. Such siloxanes and polymers can be formed in situ on the metal surface or can be pre-formed and then applied as a dilute solution to the metal surface. After drying and curing the coating protects the metal even under severely corrosive, wet and dry conditions.

The following examples illustrate the present invention:

Example 1 Approximately 0.062 mole (13.82 grams) of gamma aminopropyltriethoxysilane and about 0.062 mole (6.31 grams) of triethylamine were charged to a kettle fitted with a stirrer, condenser and dropping funnel. About 0.062 mole (14.78 grams) of (C H P(O)Cl was charged to the dropping funnel. The (C H P(O)Cl was added to the kettle slowly with stirring. The reaction was immediate and exothermic triethylamine hydrochloride preci itated out immediately upon commencement of the addition. The temperature was maintained below C. After addition Was completed the reaction mixture was filtered while warm to remove triethylamine hydrochloride (about 8.0 grams). The filtrate was a viscous, water-white liquid product similar to molasses in consistency. When cooled to room temperature the product crystallized. Elemental analysis for carbon, hydrogen, silicon, phosphorus and nitrogen and infra-red analysis confirmed the product as having the formula: (C H P(O)NH(CH Si(OC l-I The results of the elemental analysis Were as follows:

1, (C H CH P(O)Cl (1 mole, 192 grams) is reacted with delta-aminobutyl(methyl)dimethoxysilane, (1 mole, 177 grams). A viscous oily product is obtained and having the formula:

The formula for the product is confirmed by standard, elemental and infra-red analysis and by cryoscopic molecular weight determinations.

Example 3 Employing the same procedure as set forth in Example 1, C1gH37)2P(O)Ci (1 mole 589 grams) is reacted with delta aminobutyl(methyDdiethoxysilane (1 mole, 205 grams). The compound is obtained. The formula for this product is confirmed by standard, elemental and infra-red analysis and by aryoscopic molecular weight determination.

Example 4 Employing the same procedure as set forth in Example 1, when bis(N-ethylaminophenyl)diethoxysilane (1 mole, 358 grams) and ii 011150 P 01 (2 moles, 442 grams) are reacted, a product which has the formula,

is obtained' The formula for this product is confirmed by standard, elemental and infrared analysis and by aryoscopic' molecular weight determinations.

Example When one mole of a siloxane having the formula:

CH CH Hl T(CH2)aS iOSi(CH3) one mole of (C H P(O)Cl and one mole of triethylamine are dissolved in toluene and the solution is heated for 0.5 hours at 100 C. there is produced a solution which can be filtered and stripped of toluene to produce a siloxane of this invention having the formula:

The formula of this compound can be confirmed by standard infra-red and elemental analysis and cryoscopic molecular weight determinations.

Example 6 When one mole of a silane of this invention that is represented by the formula:

is dissolved in toluene and the solution so formed is mixed with one mole of water containing one percent by Weight of hydrochloric acid and the mixture so formed is maintained at about 20 C. with stirring for about twohuors, there is produced a polymer of this invention composed of groups having the formula:

The polymer so formed can be isolated by separating the toluene, ethanol and any unreacted water therefrom by heating at 40 C. and 50mm. of Hg pressure. The formula of this compound can be confirmed by standard infra-red and elemental analysis and cryoscopic molecular weight determinations.

Example When five parts by weight of either a siloxane of this invention (e.g. the siloxane produced as described in Example 5) or a polymer of this invention (e.g. the polymer produced as described in Example 6) is dissolved in 100 parts by weight of toluene and the solution so formed is sprayed on a steel surface according to conventional coating techniques, there is produced, upon volatilization of the toluene, a coating on the steel surface which protects the steel surface from corrosion.

Example 8 wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups, and the halogen-substituted monovalent hydrocarbon groups; R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the'monovalent hydrocarbon groups, R is a divalent hydrocarbon group, In is an integer that has value from 1 to 3 inclusive, n is an integer that has a value from 0 to 2 inclusive, (m+n) has a value from ,1 to 3 inclusice, p is an integer that has a value from .is an alkylene group containing from 3 to 5 carbon atoms and n is 0.

5. The hydrocarbonoxysilane of claim 1 wherein R is an alkylene group containing from 3 to 5 carbon atoms and n is 1.

6. The hydrocarbonoxysilane of claim 1 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 2.

7. The hydrocarbonoxysilane represented by the formula:

8. A siloxane comprising groups represented by the formula:

/PNR SiO (2u m 2 1 to 3 inclusive, p is an integer that has a value from 1 to 2 inclusive, and each nitrogen atom is interconnected to silicon at least three carbon atoms.

9. The siloxane of claim 8 wherein m is one and R" is an alkylene-group containing from 3 to 5 carbon atoms.

10. The siloxane of claim 3 wherein R is a hydrogen atom, m is one and R is an alkylene group containing from 3 to 5 carbon atoms.

11. The siloxane of claim 8 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 0.

12. The siloxane of claim 3 wherein R is an alkylene group containing from 3 to 5 carbon atoms and n is 1.

13. The siloxane of claim 8 wherein R" is an alkylene group containing from 3 5 carbon atoms and n is 2.

14. A siloxane comprising (a) groups represented by wherein Y is a member selected from the group conthe formula:

'sisting of the movalent hydrocarbon groups, and the halogen-substituted monovalent hydrocarbon groups, R

from 1 to 3 inclusive, n is an integer that has a value from 0 to 2 inclusive, (m+n) has a value from 1 to 3 inclusive, p is an integer that has a value from 1 to 2 rt inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms and (b) groups represented by the formula:

Rxsio wherein R has the above-defined meaning and .x is an integer that has a value from to 3.

15. The siloxane of claim 14 wherein R is a methyl group.

16. A polymer comprising polymeric units represented by the formula:

wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups, and the halogen-substituted monovalent hydrocarbon groups, R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is divalent hydrocarbon group In is an integer that has a value from 1 to 3 inclusive, n is an integer that has a value from 0 to 2 inclusive, (m-l-u) has a value from 1 to 3 inclusive, each nitrogen atom is interconnected to silicon through at least three carbon atoms; and each phosphorus atom and the silicon atom are bonded through oxygen to a member selected from the group consisting of phosphorus and silicon of another group represented by said formula.

17. The polymer of claim 16 wherein m is one and R is an alkylene group containing from 3 to 5 carbon atoms.

18. The polymer of claim 16 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 0.

19. The polymer of claim 16 wherein R" is an 'alkylene group containing from 3 to 5 carbon atoms and n is 1.

20. The polymer of claim 16 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 2.

21. The polymer of claim 16 wherein R is a methyl group and Y is an ethyl group.

22. A process for producing the polymer of claim 16 which comprises hydrolyzing and condensing a hydrocarbonoxysilane represented by the formula:

wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups, and the halogen-substituted monovalent hydrocarbon groups; R

:16 which comprises hydrolyzing and condensing a siloxane comprising groups represented by the formula:

wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups, and the halogen-substituted monovalent hydrocarbon groups, R

is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group, In is in integer that has a value from 1 to 3 inclusive, 12 is an integer that has a value from 0 to 2 inclusive, (m+n) has a value from 1 to 3 inclusive, p is an integer that has a value from 1 to 2 inclusive, and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

24. A process for producing a hydrocarbonoxysilane represented by the formula:

wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups and the halogen-substituted monovalent hydrocarbon groups, R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarben group, in is an integer that has a value from 1 to 3 inclusive, n is an integer that has a value from 0 to 2 inclusive, (m-l-n) has a value from 1 to 3 inclusive, p is an integer that has a value from 1 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms which process comprises reacting:

I. a phosphorus compound having the formula Y (I? PX (B wherein Y, R and 17 have the above-defined meanings and X is a halogen atom and H. a silane having the formula r t" [I'INR] Si(OR)3- m+n wherein R, R, R, m, n and (m-l-n) have the abovedefined meanings.

25. A process for producing a siloxane comprising groups represented by the formula:

wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups and the halogen-substituted monovalent hydrocarbon groups, R

is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group, in is an integer that has a value from 1 to 3 inclusive, n is an integer that has a value from O to 2 inclusive, (m-l-n) has a value from 1 to 3 inclusive, 2 is an integer that has a value from 1 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms which process comprises reacting:

I. a phosphorus compound having the formula wherein Y, R and 1 have the above-defined meanings and X is a halogen atom and II. a siloxane comprising groups having the formula:

wherein R, R, R", m, 3 End (m-I-n) have the above- 2,951,860 9/60 Pluedd ann 260448.2 defined meanings. 2,963,503 12/60 Marsden 26046.5 References Cited by the Examiner 2978471 4/61 Fekete 260465 UNITED STATES PATENTS 5 MURRAY TILLMAN, Primary Examiner. 2,920,094 1/ 60 Fekete 260-448.2 MILTON STERMAN, HAROLD N. BURSTEIN,

2,934,550 4/60 Jack 260448.2 WILLIAM H. SHORT, Examiners. 

8. A SILOXANE COMPRISING GROUPS REPRESENTED BY THE FORMULA: 